CHM271

PHYSICAL CHEMISTRY

CHAPTER 1 :
THERMODYNAMICS

UMI KALSUM BINTI ABDUL KARIM

umikal86@.uitm.edu.my
Student should be able to :
• 1.0 Thermodynamics
• 1.1 Types of System (open, closed, isolated)
• 1.2 First Law of Thermodynamics
• 1.2.1 Internal energy, work (pressure-volume) and heat
• 1.2.2 Specific heat and Heat capacity
• 1.2.3 Concept of Enthalpy
• 1.2.4 Effect of temperature on enthalpy
• 1.2.5 Reversible and irreversible processes
• 1.2.6 Types of thermal process (isothermal, isobaric, isochoric, adiabatic)
• 1.3 Second Law of Thermodynamics
• 1.3.1 Entropy change and spontaneity of reaction
• 1.3.2 Gibbs free energy
• 1.3.3 Dependence of entropy on variables in a system.
 INTRODUCTION
• Definition of thermodynamics: Study of energy change of
chemical/physical processes.
• Provide useful guidelines for understanding the energetic &
the direction of the process.
• Assume that the universe can be divided into a system and
its surroundings.
• The boundary can be as real as the walls of a beaker that
separates a solution from the rest of the universe
 Systems & Surroundings
the specific part of the universe
Systems
that is of interest in the study.

Surroundings the rest of the universe.

Types of Systems
Open Systems
• energy and matter can be exchanged with
the surroundings.
• Water in tumbler placed in open area

Closed Systems
• energy can be exchanged with the
surroundings, matter cannot.
• Hot water in steel box

Isolated Systems
• neither energy nor matter can be
exchanged with the surroundings.
• Hot coffee in thermos flask
 FIRST LAW OF THERMODYNAMICS

• Energy can be converted from one to another but cannot be

created or destroyed. It may change from one form to
another.
• eg; The energy lost by burning oil in power plant, may ultimately
turn up in our homes as electrical energy, heat, light and so on.

• Energy is being transferred between system & surrounding.

Hot coffee get cooled off when exposed to surroundings.

Energy lost by coffee = Energy gained by Surroundings
 INTERNAL ENERGY, E

INTERNAL ENERGY , E
• total energy of a system. (kinetic + potential)
• Sum of all kinetic & potential energies of all component of
the system.
• the energy of a system can be changed as work (w) or heat
(q).
• Units : joules (J) or calorise, 1 cal = 4.184 J
• for molar energy ; kJ mol-

CHANGE IN INTERNAL ENERGY, ΔE

• Absolute internal energy cannot measured, we can only
measure the change in internal energy
ΔE = Efinal - Einitial
 INTERNAL ENERGY, E

when a system undergoes a physical or chemical change, the

E is given by the heat absorb/release by the system plus work
done on/by the system.

ΔE = q + w

ΔE = Internal energy
q = Heat change between system & the surrounding
w = Work done on / by the surrounding
 Table 1: Sign convention for work and heat

Process Sign

Heat (q) absorbed by the surrounding (Exothermic) -

Heat (q) absorbed by the system (Endothermic) +

Work (w) done on the surrounding -

Work (w) done on the system +

** system absorbed heat, work is done on the system, internal energy of the
system increase, so both q and w are positive.
 EXERCISE
In a certain process, 600 J of work is done on the system
which gives off 250 J of heat. What is the change in
internal energy for the process (Ans:350J)
 WORK, W
Work: (w) is the energy transfer between system and surroundings
due to force acting through distance.

• Work is done when an object is moved against some opposing force.

– eg; work of expansion = gas expanding, driving force against
atmospheric pressure
• The amount of work of expansion done by the reaction:

w = - PΔV
w = work (J)
P = pressure (atm)
• ΔV = change in the volume (L)

.
example
W, For Ideal Gas Behavior
 HEAT, q

✓ Heat (q) is the energy transfer between system and

surroundings due to a temperature difference

✓ If no work is done (w = 0) by the system on its

surroundings, or vice versa, the heat given off or absorbed
by the reaction (q) would be equal to the change in the
internal energy of the system (E).

ΔE = q + w
(if and only if w = 0)
ΔE = q
 HEAT, q

w = - PΔV
ΔE = q + w
ΔE = q – PΔV

• When a reaction is carried out in constant volume

container (ΔV=0) ; the heat transferred is equal to the
change in the internal energy

ΔE = q - PΔV
ΔE = q - P(0)
ΔE = qv (at constant volume)
 HEAT, q
ΔE = q + w
ΔE = qp - PΔV
qp = ΔE + PΔV

Only under this condition of constant pressure, ΔH = qp

ΔH = ΔE + PΔV

Thus, the heat given off or absorbed during a chemical

reaction at constant pressure is equal to the change in the
enthalpy of the system.

ΔH = qp when the process

occurs under constant pressure.
 Summary

1) The heat given off or absorbed when a reaction is run at constant

volume is equal to the change in the internal energy of the system.

Δ E = qv

2) The heat given off or absorbed when a reaction is run at constant

pressure is equal to the change in the enthalpy of the system.

H = qp
ΔE = ΔH - Δ(PV)
 Heat capacity (C)

• Amount of heat required to raise the

temperature of a given quantity of the
substance by one degree Celcius.
• Unit: J/oC
• C= q /∆T
 Specific Heat Capacity (s)

• Amount of heat required to raise the

temperature of one gram of the substance
by one degree Celcius.
• Unit: J/g. oC
• c = q/mass● ∆T
• q = m c ∆T
 Molar Heat Capacity (s)

• Amount of heat required to raise the

temperature of one mole of the substance
by one degree Celcius.
• Unit: J/mol. oC
Example 2

How much heat is given off when an 869 g

iron bar cools from 940C to 50C?

C of Fe = 0.444 J/g • 0C
∆t = tfinal – tinitial = 50C – 940C = -890C

q = m C ∆T

= 869 g x 0.444 J/g • 0C x –890C

= -34,000 J
=-34 kJ
18 Concept of Enthalpy
 The heat content of the system is known as
the enthalpy of the system.
 The total heat absorbed or liberated in a
chemical reaction is called the heat of
reaction.
 We cannot measure the absolute value of
the enthalpy of the system, but we can
measure the change in enthalpy, ∆H.
 The experimental technique for measuring
enthalpy changes is called calorimetry.
 Calorimeter is a device for measuring
quantities of heat.

23
 24 Effect of temperature on
enthalpy

 Enthalpy change, ∆H - the measurement of heat at constant pressure,

qp (difference of heat content between products & reactants, unit
kJ/mol)
 Heat capacity, C - amount of heat required to raise the temperature of
a substance by 1K
C= q/∆T
 Specific heat of a substance, c is the quantity of heat required to raise
the temperature of 1g substance by 1K
c= q/mass● ∆T
 Heat, q= mc ∆T
 REVERSIBLE PROCESS

• Reversible process occur when the backwards reaction

(products → reactants) takes place relatively easily under certain
conditions.
• The products can react to produce the original reactants again.

• Can restore both system and surroundings to their initial state.

• Reversible changes, like melting and dissolving, can be changed

back again. Mixtures can be separated out by methods like filtering
and evaporating.
 IRREVERSIBLE PROCESS

• Most chemical reactions are considered irreversible – the products

that are made cannot readily be changed back into their reactants.

• They go to completion and cannot be reversed easily.

• System and its surroundings cannot both be restored to their initial

conditions

• All spontaneous processes are irreversible.

• All real processes are irreversible.

• Example of an irreversible process is the direct transfer of heat

from a hot object to a cold object and burning.
 TYPE OF THERMAL PROCESS

• An adiabatic process is a process during which no heat enters or

leaves the system.

• An isobaric process is a process that occurs at constant pressure.

• An isochoric process is a process that takes place at constant

volume

• An isothermal process occurs at constant temperature.

 Exercise

A gas is expanding from 2.0 L to 6.0 L at a constant pressure of

1.2 atm. Calculate the change in internal energy if the process is
adiabatic process?
 SECOND LAW OF THERMODYNAMICS

➢ The entropy of the universe increases in a spontaneous

process and remains unchanged in an equilibrium
process.

Spontaneous process: Suniv = Ssys + Ssurr > 0

Equilibrium process: Suniv = Ssys + Ssurr = 0

 SPONTANEITY

SPONTANEOUS PROCESSES
▪ A reaction which occur under the given set of condition
▪ processes are those that can proceed without any outside intervention.

NON SPONTANEOUS PROCESSES

▪ A reaction does not occur under specified conditions.

Spontaneous Non Spontaneous

A ball rolling downhill A ball rolling uphill
Sugar dissolves in water form Dissolved sugar reappear in original
Iron forms rust Rust change back to iron

✓ LARGE numbers of exothermic reactions are spontaneous.

✓ Even though exothermicity favors the spontaneity but does not guarantee it.
✓ Need another thermodynamic quantity : ENTROPY
 ENTROPY, S

• Measure of the randomness or disorder of a system.

• Greater the disorder of a system, the greater its entropy
• More ordered a system, the smaller its entropy.
• For any substance, the solid state is more ordered than the liquid state
and the liquid state is more ordered than gas state
• S0 must be positive value for the reaction to be spontaneous/favorable.

Ssolid < Sliquid

Sliquid < Sgas

Processes that lead to an increase in entropy (S > 0)
 STANDARD ENTROPY, S°

• The absolute entropy of a substance at standard condition.

• Units : J/K or J/K mol

• If S0 is positive value, the reaction is

spontaneous/favorable.
 Entropy Changes

• In general, entropy increases when

– Gases are formed from liquids and
solids.
– Liquids or solutions are formed
from solids.
– The number of gas molecules
increases.
• The number of moles increases.
• If a reaction produces more gas
molecules than it consumes, ΔS0 > 0.
• If the total number of gas molecules
diminishes, ΔS0 < 0.
 Predict the processes that will lead to an
example increase in the entropy of the system.

a)N2(g) + 3H2 (g) ⇋ 2 NH3(g)

The entropy of the system therefore decreases due to the total number of
molecules decreases in this reaction. Thus, the system becomes more ordered.

b)H2O(l) ⇋ H2O(g)
Gases are more disordered than the corresponding liquids, so the entropy of the
system increases

c)CaCO3(s) → CaO(s) + CO2(g)

Reactions in which a compound decomposes into two products lead to an
increase in entropy because the system becomes more disordered. The increase
in entropy in this reaction is even larger because the starting material is a solid
and one of the products is a gas.

d)NH4NO3(s) + H2O(l) → NH4+ (aq) + NO3- (aq)

The NH4+ and NO3- ions are free to move in a random fashion through the
aqueous solution, whereas these ions are locked into position in the crystal. As a
result, the entropy of the system increases in this
 SPONTANEITY

• The standard entropy of reaction (ΔS° ) is the entropy

change for a reaction carried out at 1 atm and 25°C.

aA + bB → cC + dD

ΔS° rxn = ∑nS° (products) - ∑nS° (reactants)

ΔS° rxn = [cS°(C) + dS°(D)] - [aS°(A) + bS°(B)]

• S° for each component is found in a table.

example
Calculate the standard entropy change for the following
reaction at 250C.

2CO (g) + O2 (g) → 2CO2 (g)

S°(CO) = 197.9 J/K mol S°(CO2) = 213.6 J/K mol

S°(O2) = 205.0 J/K mol

∆S°rxn= [2 x S° (CO2)] – [2 x S° (CO) + S0 (O2)]

∆S°rxn= [2 x 213.6] – [(2 x 197.9)+ 205]
∆S°rxn = 427.2 – [395.8 + 205.0]

= -173.6 J/K
 EXERCISE

• Calculate the standard entropy changes for the

following reactions at 25oC.
(Ans = 20 J/K.mol)

H2 (g) + Cl2 (g) 2HCl (g)

So (H2) = 131 J/K.mol

So (Cl2) = 223 J/K.mol
So (HCl) = 187 J/K.mol
 RELATIONSHIP OF ΔS & ΔH

• We can express ΔS surr in terms of the enthalpy change for the system, ΔH, as
follows:

ΔH in joules (J)
T in Kelvins ( + 273.15)

Example;

Calculate ΔSsurr and ΔSuniv for the vaporization of 1.00 mole of water at 125°C.
(ΔH=40.7 kJ/mol, and ΔSsys= 119 J/K for 1 mole of water vaporizing.)
Solution

ΔS = ΔS + ΔS
univ surr sys

ΔS =- 102.22 J/K mol + 119 J / K.mol

univ

ΔS = +16.78J / K.mol
univ
 The variation of entropy (Gas)

At constant temperature

At constant pressure

At constant volume
example
ex 1 :Determine the change in entropy for 1.0 mole of an ideal gas volume
500 L is allowed to expand to 1000L

ex 2 :Calculate the entropy change when argon at 25°C in a container

volume 0.5 dm3 is heated to 100°C. (Cv = 12.47 JK-1mol-1).
 EXERCISE
QUESTION 1
Predict whether the entropy change of the system in each of the
following reaction is positive or negative.
i.2H2 (g) + O2 (g) → 2H2O (l)
ii.NH4Cl (s) → NH3 (g) + HCl (g)
iii.H2 (g) + Br2 (g) → 2HBr (g)

QUESTION 2
The equation for the decomposition of zinc carbonate is:
ZnCO3 (s) → ZnO (s) + CO2 (g)

The values for ΔS˚sys and ΔS˚surr are +175 J mol-1 K-1 and -238 J
mol-1 K-1, respectively. Show that the reaction is not spontaneous at
298 K.
 GIBBS FREE ENERGY

❖ Some reactions are spontaneous because they give off energy in the form of heat
(∆H < 0, Exothermic), Others are spontaneous because they lead to an increase
in the disorder of the system (∆ S > 0).

❖ What happens when one of the potential driving forces behind a chemical reaction
is favorable and the other is not?

❖ new quantity known as the Gibbs free energy (G) of the system, which reflects
the balance between these forces.

• Gibbs free energy (G) is the energy available to do useful work

• any reaction for which ∆ Go is negative should be favorable, or spontaneous.

 GIBBS FREE ENERGY
enthalpy of the system minus the change in the product of the temperature times
the entropy of the system.
G = Hsys –TSsys

If the data are collected under standard-state conditions, the result is the
standard-state free energy of reaction (Go).
G° = H ° sys –TS ° sys

Favorable/spontaneous Unfavorable/Non
spontaneous
G° - +
H° - (exo) + (endo)
S° + -

• ΔG=0, the reaction/process is at equilibrium (neither the

forward nor the reverse process is favored).
example
Calculate ∆H° and ∆S° for the following reaction:

N2(g) + 3 H2(g) → 2 NH3(g)

Use the results of this calculation to determine the value of Go for this
reaction at 25o C, is the reaction occur spontaneously or

o
Compound ∆Hf (kJ/mol) ∆S° (J/K.mol)
N2(g) 191.61
H2(g) 130.68
NH3(g) -46.11 192.45
∆Ho = ∆ Hfo(products) - ∆ Hfo(reactants)
= [2 mol x -46.11 kJ/mol] - [0kJ/mol]
= -92,220 J
This reaction is exothermic, and the enthalpy of reaction is therefore favorable:

∆ So = ∆ So(products) - ∆ So(reactants)
= [2 mol x 192.45 J/mol.K] - [(1 mol x191.61 J/mol.K) + (3 mol x 130.68 J/mol.K)]
= -198.75 J/K
The reaction unfavored by the entropy of reaction:

To decide whether it occur spontaneously or not we have to compare the ∆ Go

∆ Go = ∆ Ho - T ∆So
= -92,220 J - (298.15 K x -198.75 J/K)
= -92,220 J – (-59257.31) J
= -33 kJ

At 25o C, the standard-state free energy for this reaction is negative,

The reaction is therefore spontaneous at room temperature.
 PRACTICE
Calculate the standard free energy change for the formation of NO(g) from N2(g)
and O2(g) at 298 K:
N2(g) + O2(g) → 2 NO(g)

given that ΔH° = 180.7 kJ and ΔS° = 24.7 J/K. Is the reaction spontaneous under
these circumstances?

‘
 Affect of Temperature on Spontaneity

ΔH ΔS ΔG Reaction Outcome T dependence

− + Always Reaction is spontaneous at all No
negative temperatures
+ − Always Reaction is nonspontaneous at all No
positive temperatures.
− − - at low T Reaction is spontaneous at low T,
+ at high T but become nonspontaneous at Yes
high T.
+ + + at low T Reaction is nonspontaneous at Yes
- at high T low T, but becomes spontaneous
at high T.
 Determine the temperature at which a process is spontaneous

• To determine that temperature, we must set ∆G equal to 0

G = H − TS
0 = H − TS

H − TS  0 (Spontaneous reaction)

H − TS  0 (Non Spontaneous reaction)
eg ; For a reaction in which ∆H = 199.5 kJ/mol and ∆S = 476 J/K ∙ mol,
determine the temperature (in °C) above which the reaction is spontaneous.

H − TS  0

199.5kJ / mol − ( T x 0.476kJ / K .mol )  0

− 199.5kJ / mol
T
− 0.476kJ / K .mol T  419K
T = 419 − 273.15
T  145.8 C
Phase Transitions Between Physical States
At the temperature at which the phase transition occurs, the system is at
equilibrium:
G = H − TS
0 = H − TS
H
S =
T

eg :For the reaction below, find ∆S if the reaction occur at 65°C.

H2O (l) ⇋ H2O (g) ∆H=40.79 kJ/mol

H
S =
T
40.79kJ / mol
S =
338.15K
S = 120J / K.mol
 Calculating Free Energy Changes

• ΔG°f =0 for elements in their standard states (their naturally

occurring form at 25°C)

• standard free energy of formation (ΔG°f )

is the free-energy change for the formation of 1 mole of the substance
from its elements in their standard states,

• Substances with negative values for ΔG°f are stable and do not
decompose into their constituent elements.

• can use a table of standard free energy of formation values (ΔG°f )

for reactants and products to calculate standard free energy
changes (ΔG°)

ΔG°= ΔG°f product - ΔG°f reactant